CA2261174C - Olefin polymerization catalyst composition comprising group 13 compound - Google Patents
Olefin polymerization catalyst composition comprising group 13 compound Download PDFInfo
- Publication number
- CA2261174C CA2261174C CA002261174A CA2261174A CA2261174C CA 2261174 C CA2261174 C CA 2261174C CA 002261174 A CA002261174 A CA 002261174A CA 2261174 A CA2261174 A CA 2261174A CA 2261174 C CA2261174 C CA 2261174C
- Authority
- CA
- Canada
- Prior art keywords
- group
- bonded
- hydrocarbyl
- catalyst composition
- borate
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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- 239000000203 mixture Substances 0.000 title claims abstract description 61
- 150000001875 compounds Chemical class 0.000 title claims abstract description 23
- 150000001336 alkenes Chemical class 0.000 title description 7
- 239000002685 polymerization catalyst Substances 0.000 title description 7
- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 title description 5
- 239000003054 catalyst Substances 0.000 claims abstract description 55
- 125000001183 hydrocarbyl group Chemical group 0.000 claims abstract description 21
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 21
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 18
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 13
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 12
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 7
- 239000010703 silicon Substances 0.000 claims abstract description 7
- 229910021482 group 13 metal Inorganic materials 0.000 claims abstract description 4
- -1 cyclopentadienyl- Chemical group 0.000 claims description 58
- 238000000034 method Methods 0.000 claims description 34
- 238000006116 polymerization reaction Methods 0.000 claims description 29
- 230000003213 activating effect Effects 0.000 claims description 24
- 230000003647 oxidation Effects 0.000 claims description 24
- 238000007254 oxidation reaction Methods 0.000 claims description 24
- 229910052751 metal Inorganic materials 0.000 claims description 22
- 239000002184 metal Substances 0.000 claims description 22
- 239000003446 ligand Substances 0.000 claims description 20
- 239000000178 monomer Substances 0.000 claims description 19
- 125000000129 anionic group Chemical group 0.000 claims description 16
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims description 16
- 230000007935 neutral effect Effects 0.000 claims description 10
- 125000004429 atom Chemical group 0.000 claims description 8
- 125000001424 substituent group Chemical group 0.000 claims description 6
- ARQZVYIDGOAZGG-UHFFFAOYSA-N 1-[[bis(trimethylsilyl)amino]-(2-methylpropyl)alumanyl]-2-methylpropane Chemical compound CC(C)C[Al+]CC(C)C.C[Si](C)(C)[N-][Si](C)(C)C ARQZVYIDGOAZGG-UHFFFAOYSA-N 0.000 claims description 5
- 239000002879 Lewis base Substances 0.000 claims description 5
- 238000012644 addition polymerization Methods 0.000 claims description 5
- 150000007527 lewis bases Chemical class 0.000 claims description 5
- 230000000737 periodic effect Effects 0.000 claims description 5
- 239000007795 chemical reaction product Substances 0.000 claims description 3
- FZHAPNGMFPVSLP-UHFFFAOYSA-N silanamine Chemical compound [SiH3]N FZHAPNGMFPVSLP-UHFFFAOYSA-N 0.000 claims description 3
- VIDOIAMNUYKVQY-UHFFFAOYSA-N [[bis(trimethylsilyl)amino]-ethylalumanyl]ethane Chemical compound CC[Al](CC)N([Si](C)(C)C)[Si](C)(C)C VIDOIAMNUYKVQY-UHFFFAOYSA-N 0.000 claims description 2
- VDYHSMFDGHZHEY-UHFFFAOYSA-N bis(2-methylpropyl)alumanylium;bis(2-methylpropyl)azanide Chemical compound CC(C)C[N-]CC(C)C.CC(C)C[Al+]CC(C)C VDYHSMFDGHZHEY-UHFFFAOYSA-N 0.000 claims description 2
- DOYHJUUCQNMLBS-UHFFFAOYSA-N bis(2-methylpropyl)alumanylium;diethylazanide Chemical compound CC[N-]CC.CC(C)C[Al+]CC(C)C DOYHJUUCQNMLBS-UHFFFAOYSA-N 0.000 claims description 2
- HQBJDUAFPFFAMB-UHFFFAOYSA-N bis(2-methylpropyl)azanide;di(propan-2-yl)alumanylium Chemical compound CC(C)[Al+]C(C)C.CC(C)C[N-]CC(C)C HQBJDUAFPFFAMB-UHFFFAOYSA-N 0.000 claims description 2
- WZAKEHLZCUZFGI-UHFFFAOYSA-N bis(2-methylpropyl)azanide;diethylalumanylium Chemical compound CC[Al+]CC.CC(C)C[N-]CC(C)C WZAKEHLZCUZFGI-UHFFFAOYSA-N 0.000 claims description 2
- AHIXBAUKXXNQKR-UHFFFAOYSA-N bis(2-methylpropyl)azanide;dimethylalumanylium Chemical compound C[Al+]C.CC(C)C[N-]CC(C)C AHIXBAUKXXNQKR-UHFFFAOYSA-N 0.000 claims description 2
- HJCKDIPUPUIBNF-UHFFFAOYSA-N bis(trimethylsilyl)azanide;dimethylalumanylium Chemical compound C[Al+]C.C[Si](C)(C)[N-][Si](C)(C)C HJCKDIPUPUIBNF-UHFFFAOYSA-N 0.000 claims description 2
- UORVGPXVDQYIDP-BJUDXGSMSA-N borane Chemical class [10BH3] UORVGPXVDQYIDP-BJUDXGSMSA-N 0.000 claims description 2
- GTLMIIKASNFJDX-UHFFFAOYSA-N diethylalumanylium;dimethylazanide Chemical compound C[N-]C.CC[Al+]CC GTLMIIKASNFJDX-UHFFFAOYSA-N 0.000 claims description 2
- BPNXIRKNLAUWLF-UHFFFAOYSA-N diethylazanide;di(propan-2-yl)alumanylium Chemical compound CC[N-]CC.CC(C)[Al+]C(C)C BPNXIRKNLAUWLF-UHFFFAOYSA-N 0.000 claims description 2
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 claims description 2
- 125000001207 fluorophenyl group Chemical group 0.000 claims description 2
- SSAWPNVUGVLDQP-UHFFFAOYSA-N n-diethylalumanyl-n-ethylethanamine Chemical compound CC[N-]CC.CC[Al+]CC SSAWPNVUGVLDQP-UHFFFAOYSA-N 0.000 claims description 2
- VJDWAJKRQRWSCK-UHFFFAOYSA-N n-dimethylalumanyl-n-ethylethanamine Chemical compound CCN(CC)[Al](C)C VJDWAJKRQRWSCK-UHFFFAOYSA-N 0.000 claims description 2
- GUHSGHQVNSDCNV-UHFFFAOYSA-N n-dimethylalumanyl-n-methylmethanamine Chemical group CN(C)[Al](C)C GUHSGHQVNSDCNV-UHFFFAOYSA-N 0.000 claims description 2
- UPQPGDKNNDRHME-UHFFFAOYSA-N bis(2-methylpropyl)alumanylium;dimethylazanide Chemical compound C[N-]C.CC(C)C[Al+]CC(C)C UPQPGDKNNDRHME-UHFFFAOYSA-N 0.000 claims 1
- VSMPRTIVALMNNA-UHFFFAOYSA-N dimethylazanide;di(propan-2-yl)alumanylium Chemical compound C[N-]C.CC(C)[Al+]C(C)C VSMPRTIVALMNNA-UHFFFAOYSA-N 0.000 claims 1
- 125000005843 halogen group Chemical group 0.000 claims 1
- 239000002574 poison Substances 0.000 abstract description 4
- 231100000614 poison Toxicity 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 3
- 150000002736 metal compounds Chemical class 0.000 abstract 1
- BTBUEUYNUDRHOZ-UHFFFAOYSA-N Borate Chemical compound [O-]B([O-])[O-] BTBUEUYNUDRHOZ-UHFFFAOYSA-N 0.000 description 38
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 35
- 150000001450 anions Chemical class 0.000 description 27
- 125000000538 pentafluorophenyl group Chemical group FC1=C(F)C(F)=C(*)C(F)=C1F 0.000 description 27
- 239000002904 solvent Substances 0.000 description 19
- 229920000642 polymer Polymers 0.000 description 18
- 150000001993 dienes Chemical class 0.000 description 15
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 13
- 239000005977 Ethylene Substances 0.000 description 13
- 238000005868 electrolysis reaction Methods 0.000 description 12
- 238000006243 chemical reaction Methods 0.000 description 11
- 239000003115 supporting electrolyte Substances 0.000 description 11
- 150000001768 cations Chemical class 0.000 description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 10
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 9
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 9
- OFBQJSOFQDEBGM-UHFFFAOYSA-N n-pentane Natural products CCCCC OFBQJSOFQDEBGM-UHFFFAOYSA-N 0.000 description 9
- 125000002091 cationic group Chemical group 0.000 description 8
- 239000001257 hydrogen Substances 0.000 description 8
- 229910052739 hydrogen Inorganic materials 0.000 description 8
- 230000001976 improved effect Effects 0.000 description 8
- 150000002500 ions Chemical class 0.000 description 8
- KWKAKUADMBZCLK-UHFFFAOYSA-N 1-octene Chemical compound CCCCCCC=C KWKAKUADMBZCLK-UHFFFAOYSA-N 0.000 description 7
- 229930195733 hydrocarbon Natural products 0.000 description 7
- 150000003839 salts Chemical class 0.000 description 7
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 6
- 125000003118 aryl group Chemical group 0.000 description 6
- JLTDJTHDQAWBAV-UHFFFAOYSA-O dimethyl(phenyl)azanium Chemical compound C[NH+](C)C1=CC=CC=C1 JLTDJTHDQAWBAV-UHFFFAOYSA-O 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 description 6
- TVMXDCGIABBOFY-UHFFFAOYSA-N n-Octanol Natural products CCCCCCCC TVMXDCGIABBOFY-UHFFFAOYSA-N 0.000 description 6
- 239000002002 slurry Substances 0.000 description 6
- ZOXJGFHDIHLPTG-UHFFFAOYSA-N Boron Chemical compound [B] ZOXJGFHDIHLPTG-UHFFFAOYSA-N 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 5
- 229910052796 boron Inorganic materials 0.000 description 5
- 125000004122 cyclic group Chemical group 0.000 description 5
- 239000003085 diluting agent Substances 0.000 description 5
- 150000002170 ethers Chemical class 0.000 description 5
- 125000001475 halogen functional group Chemical group 0.000 description 5
- 150000002430 hydrocarbons Chemical class 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- 238000004519 manufacturing process Methods 0.000 description 5
- 239000000243 solution Substances 0.000 description 5
- 229910052726 zirconium Inorganic materials 0.000 description 5
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 4
- WSSSPWUEQFSQQG-UHFFFAOYSA-N 4-methyl-1-pentene Chemical compound CC(C)CC=C WSSSPWUEQFSQQG-UHFFFAOYSA-N 0.000 description 4
- 229920000089 Cyclic olefin copolymer Polymers 0.000 description 4
- 229920002943 EPDM rubber Polymers 0.000 description 4
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 description 4
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical group [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 4
- QCWXUUIWCKQGHC-UHFFFAOYSA-N Zirconium Chemical group [Zr] QCWXUUIWCKQGHC-UHFFFAOYSA-N 0.000 description 4
- 230000004913 activation Effects 0.000 description 4
- 150000001335 aliphatic alkanes Chemical class 0.000 description 4
- 150000003863 ammonium salts Chemical class 0.000 description 4
- 125000004432 carbon atom Chemical group C* 0.000 description 4
- DMEGYFMYUHOHGS-UHFFFAOYSA-N cycloheptane Chemical compound C1CCCCCC1 DMEGYFMYUHOHGS-UHFFFAOYSA-N 0.000 description 4
- 238000010528 free radical solution polymerization reaction Methods 0.000 description 4
- 229910052735 hafnium Chemical group 0.000 description 4
- VBJZVLUMGGDVMO-UHFFFAOYSA-N hafnium atom Chemical group [Hf] VBJZVLUMGGDVMO-UHFFFAOYSA-N 0.000 description 4
- NNPPMTNAJDCUHE-UHFFFAOYSA-N isobutane Chemical compound CC(C)C NNPPMTNAJDCUHE-UHFFFAOYSA-N 0.000 description 4
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 4
- 239000000047 product Substances 0.000 description 4
- 229910052719 titanium Inorganic materials 0.000 description 4
- 239000010936 titanium Substances 0.000 description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N Alumina Chemical class [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 3
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
- 239000002671 adjuvant Substances 0.000 description 3
- 150000001338 aliphatic hydrocarbons Chemical class 0.000 description 3
- 125000000217 alkyl group Chemical group 0.000 description 3
- 229910052782 aluminium Inorganic materials 0.000 description 3
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 3
- 238000006758 bulk electrolysis reaction Methods 0.000 description 3
- 239000001273 butane Substances 0.000 description 3
- 239000004020 conductor Substances 0.000 description 3
- BOXSCYUXSBYGRD-UHFFFAOYSA-N cyclopenta-1,3-diene;iron(3+) Chemical class [Fe+3].C=1C=C[CH-]C=1.C=1C=C[CH-]C=1 BOXSCYUXSBYGRD-UHFFFAOYSA-N 0.000 description 3
- 125000003800 germyl group Chemical group [H][Ge]([H])([H])[*] 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 150000004820 halides Chemical class 0.000 description 3
- 150000002738 metalloids Chemical group 0.000 description 3
- IJDNQMDRQITEOD-UHFFFAOYSA-N n-butane Chemical compound CCCC IJDNQMDRQITEOD-UHFFFAOYSA-N 0.000 description 3
- VFLWKHBYVIUAMP-UHFFFAOYSA-N n-methyl-n-octadecyloctadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCCCC VFLWKHBYVIUAMP-UHFFFAOYSA-N 0.000 description 3
- 239000007800 oxidant agent Substances 0.000 description 3
- 150000003254 radicals Chemical class 0.000 description 3
- SCABQASLNUQUKD-UHFFFAOYSA-N silylium Chemical compound [SiH3+] SCABQASLNUQUKD-UHFFFAOYSA-N 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- PRBHEGAFLDMLAL-GQCTYLIASA-N (4e)-hexa-1,4-diene Chemical compound C\C=C\CC=C PRBHEGAFLDMLAL-GQCTYLIASA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- XWJBRBSPAODJER-UHFFFAOYSA-N 1,7-octadiene Chemical compound C=CCCCCC=C XWJBRBSPAODJER-UHFFFAOYSA-N 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 2
- AFFLGGQVNFXPEV-UHFFFAOYSA-N 1-decene Chemical compound CCCCCCCCC=C AFFLGGQVNFXPEV-UHFFFAOYSA-N 0.000 description 2
- LDTAOIUHUHHCMU-UHFFFAOYSA-N 3-methylpent-1-ene Chemical compound CCC(C)C=C LDTAOIUHUHHCMU-UHFFFAOYSA-N 0.000 description 2
- BBDKZWKEPDTENS-UHFFFAOYSA-N 4-Vinylcyclohexene Chemical compound C=CC1CCC=CC1 BBDKZWKEPDTENS-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 239000007848 Bronsted acid Substances 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical class S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 description 2
- XTHFKEDIFFGKHM-UHFFFAOYSA-N Dimethoxyethane Chemical compound COCCOC XTHFKEDIFFGKHM-UHFFFAOYSA-N 0.000 description 2
- OTMSDBZUPAUEDD-UHFFFAOYSA-N Ethane Chemical compound CC OTMSDBZUPAUEDD-UHFFFAOYSA-N 0.000 description 2
- YNQLUTRBYVCPMQ-UHFFFAOYSA-N Ethylbenzene Chemical compound CCC1=CC=CC=C1 YNQLUTRBYVCPMQ-UHFFFAOYSA-N 0.000 description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 2
- 239000002841 Lewis acid Substances 0.000 description 2
- KWYHDKDOAIKMQN-UHFFFAOYSA-N N,N,N',N'-tetramethylethylenediamine Chemical compound CN(C)CCN(C)C KWYHDKDOAIKMQN-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 2
- ATUOYWHBWRKTHZ-UHFFFAOYSA-N Propane Chemical compound CCC ATUOYWHBWRKTHZ-UHFFFAOYSA-N 0.000 description 2
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- 150000001342 alkaline earth metals Chemical class 0.000 description 2
- 150000001412 amines Chemical class 0.000 description 2
- 150000001491 aromatic compounds Chemical class 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- 125000001797 benzyl group Chemical group [H]C1=C([H])C([H])=C(C([H])=C1[H])C([H])([H])* 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 150000001642 boronic acid derivatives Chemical class 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 239000011951 cationic catalyst Substances 0.000 description 2
- 239000003638 chemical reducing agent Substances 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 125000004093 cyano group Chemical group *C#N 0.000 description 2
- LPIQUOYDBNQMRZ-UHFFFAOYSA-N cyclopentene Chemical compound C1CC=CC1 LPIQUOYDBNQMRZ-UHFFFAOYSA-N 0.000 description 2
- PBGGNZZGJIKBMJ-UHFFFAOYSA-N di(propan-2-yl)azanide Chemical compound CC(C)[N-]C(C)C PBGGNZZGJIKBMJ-UHFFFAOYSA-N 0.000 description 2
- LDLDYFCCDKENPD-UHFFFAOYSA-N ethenylcyclohexane Chemical compound C=CC1CCCCC1 LDLDYFCCDKENPD-UHFFFAOYSA-N 0.000 description 2
- 229920001519 homopolymer Polymers 0.000 description 2
- 230000001965 increasing effect Effects 0.000 description 2
- 239000001282 iso-butane Substances 0.000 description 2
- QWTDNUCVQCZILF-UHFFFAOYSA-N isopentane Chemical compound CCC(C)C QWTDNUCVQCZILF-UHFFFAOYSA-N 0.000 description 2
- 150000007517 lewis acids Chemical class 0.000 description 2
- 229910052744 lithium Inorganic materials 0.000 description 2
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 2
- JZBZLRKFJWQZHU-UHFFFAOYSA-N n,n,2,4,6-pentamethylaniline Chemical compound CN(C)C1=C(C)C=C(C)C=C1C JZBZLRKFJWQZHU-UHFFFAOYSA-N 0.000 description 2
- UWHRNIXHZAWBMF-UHFFFAOYSA-N n-dodecyl-n-methyldodecan-1-amine Chemical compound CCCCCCCCCCCCN(C)CCCCCCCCCCCC UWHRNIXHZAWBMF-UHFFFAOYSA-N 0.000 description 2
- KCMTVIZYKDBFFS-UHFFFAOYSA-N n-hexadecyl-n-methylhexadecan-1-amine Chemical compound CCCCCCCCCCCCCCCCN(C)CCCCCCCCCCCCCCCC KCMTVIZYKDBFFS-UHFFFAOYSA-N 0.000 description 2
- SJYNFBVQFBRSIB-UHFFFAOYSA-N norbornadiene Chemical compound C1=CC2C=CC1C2 SJYNFBVQFBRSIB-UHFFFAOYSA-N 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 230000000379 polymerizing effect Effects 0.000 description 2
- 229920000098 polyolefin Polymers 0.000 description 2
- 229910052700 potassium Inorganic materials 0.000 description 2
- 239000011591 potassium Substances 0.000 description 2
- 239000012429 reaction media Substances 0.000 description 2
- 239000000377 silicon dioxide Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 230000000087 stabilizing effect Effects 0.000 description 2
- RWSOTUBLDIXVET-UHFFFAOYSA-O sulfonium Chemical compound [SH3+] RWSOTUBLDIXVET-UHFFFAOYSA-O 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N tetrahydrofuran Natural products C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- IMFACGCPASFAPR-UHFFFAOYSA-N tributylamine Chemical compound CCCCN(CCCC)CCCC IMFACGCPASFAPR-UHFFFAOYSA-N 0.000 description 2
- ZMANZCXQSJIPKH-UHFFFAOYSA-O triethylammonium ion Chemical compound CC[NH+](CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-O 0.000 description 2
- YWWDBCBWQNCYNR-UHFFFAOYSA-N trimethylphosphine Chemical compound CP(C)C YWWDBCBWQNCYNR-UHFFFAOYSA-N 0.000 description 2
- RIOQSEWOXXDEQQ-UHFFFAOYSA-N triphenylphosphine Chemical compound C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 RIOQSEWOXXDEQQ-UHFFFAOYSA-N 0.000 description 2
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Classifications
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- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
- B01J31/1805—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms the ligands containing nitrogen
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/52—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides selected from boron, aluminium, gallium, indium, thallium or rare earths
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- B01J31/02—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides
- B01J31/12—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides
- B01J31/14—Catalysts comprising hydrides, coordination complexes or organic compounds containing organic compounds or metal hydrides containing organo-metallic compounds or metal hydrides of aluminium or boron
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- B01J31/2282—Unsaturated compounds used as ligands
- B01J31/2295—Cyclic compounds, e.g. cyclopentadienyls
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/40—Complexes comprising metals of Group IV (IVA or IVB) as the central metal
- B01J2531/49—Hafnium
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
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- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
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- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65908—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an ionising compound other than alumoxane, e.g. (C6F5)4B-X+
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- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
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- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/65912—Component covered by group C08F4/64 containing a transition metal-carbon bond in combination with an organoaluminium compound
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F4/00—Polymerisation catalysts
- C08F4/42—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors
- C08F4/44—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides
- C08F4/60—Metals; Metal hydrides; Metallo-organic compounds; Use thereof as catalyst precursors selected from light metals, zinc, cadmium, mercury, copper, silver, gold, boron, gallium, indium, thallium, rare earths or actinides together with refractory metals, iron group metals, platinum group metals, manganese, rhenium technetium or compounds thereof
- C08F4/62—Refractory metals or compounds thereof
- C08F4/64—Titanium, zirconium, hafnium or compounds thereof
- C08F4/659—Component covered by group C08F4/64 containing a transition metal-carbon bond
- C08F4/6592—Component covered by group C08F4/64 containing a transition metal-carbon bond containing at least one cyclopentadienyl ring, condensed or not, e.g. an indenyl or a fluorenyl ring
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S526/00—Synthetic resins or natural rubbers -- part of the class 520 series
- Y10S526/943—Polymerization with metallocene catalysts
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- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Inorganic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Transition And Organic Metals Composition Catalysts For Addition Polymerization (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US2206196P | 1996-07-23 | 1996-07-23 | |
US60/022,061 | 1996-07-23 | ||
PCT/US1997/012649 WO1998003558A1 (en) | 1996-07-23 | 1997-07-18 | Olefin polymerization catalyst composition comprising group 13 compound |
Publications (2)
Publication Number | Publication Date |
---|---|
CA2261174A1 CA2261174A1 (en) | 1998-01-29 |
CA2261174C true CA2261174C (en) | 2005-11-29 |
Family
ID=21807620
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CA002261174A Expired - Fee Related CA2261174C (en) | 1996-07-23 | 1997-07-18 | Olefin polymerization catalyst composition comprising group 13 compound |
Country Status (17)
Country | Link |
---|---|
US (1) | US6017842A (zh) |
EP (1) | EP0914353B1 (zh) |
JP (1) | JP2000514858A (zh) |
KR (1) | KR100466733B1 (zh) |
CN (1) | CN1092668C (zh) |
AR (1) | AR010516A1 (zh) |
AU (1) | AU718544B2 (zh) |
BR (1) | BR9710511A (zh) |
CA (1) | CA2261174C (zh) |
CZ (1) | CZ293472B6 (zh) |
DE (1) | DE69715213T2 (zh) |
ES (1) | ES2177995T3 (zh) |
HU (1) | HU223376B1 (zh) |
PL (1) | PL331324A1 (zh) |
TR (1) | TR199900080T2 (zh) |
TW (1) | TW434271B (zh) |
WO (1) | WO1998003558A1 (zh) |
Families Citing this family (25)
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US6294625B1 (en) * | 1990-03-20 | 2001-09-25 | Exxonmobil Chemical Patents Inc. | Catalyst system of enhanced productivity and its use in polymerization process |
KR20010032116A (ko) * | 1997-12-01 | 2001-04-16 | 보 구스타프쏜 | 수분 흡수 장치 |
EP1090045B1 (en) | 1998-06-12 | 2004-04-28 | Univation Technologies LLC | Olefin polymerization process using activated lewis acid-base complexes |
EP1097175B1 (en) | 1998-07-16 | 2007-02-28 | Univation Technologies LLC | Aluminum-based lewis acid cocatalysts for olefin polymerization |
EP1105398B1 (en) | 1998-08-17 | 2002-07-17 | The Dow Chemical Company | Activator composition comprising aluminum compound mixture |
DE69905728T2 (de) * | 1998-08-17 | 2003-12-24 | Dow Global Technologies, Inc. | Drei-koordinierte alluminium-katalysatoraktivatorverbindung |
US6559088B1 (en) * | 1999-02-22 | 2003-05-06 | Fina Technology, Inc. | Ziegler-Natta catalyst with amine for polymerization |
BE1012568A3 (fr) * | 1999-03-24 | 2000-12-05 | Solvay | Procede pour la polymerisation des alphaolefines. |
US6476164B1 (en) | 1999-10-22 | 2002-11-05 | Exxonmobil Chemical Patents Inc. | Carbenium cationic complexes suitable for polymerization catalysts |
US6475946B1 (en) | 1999-10-22 | 2002-11-05 | Exxonmobil Chemical Patents Inc. | Olefin polymerization catalysis with aryl substituted carbenium cationic complexes |
US6822057B2 (en) | 1999-12-09 | 2004-11-23 | Exxon Mobil Chemical Patents Inc. | Olefin polymerization catalysts derived from Group-15 cationic compounds and processes using them |
ES2249320T3 (es) * | 1999-12-09 | 2006-04-01 | Exxonmobil Chemical Patents Inc. | Cocatalizadores para la polimerizacion de olefinas derivados de compuestos cationicos del grupo 15 y procesos que los utilizan. |
US6489480B2 (en) | 1999-12-09 | 2002-12-03 | Exxonmobil Chemical Patents Inc. | Group-15 cationic compounds for olefin polymerization catalysts |
WO2001046273A1 (en) | 1999-12-20 | 2001-06-28 | Exxon Chemical Patents Inc. | Processes for the preparation polyolefin resins using supported ionic catalysts |
JP2002293818A (ja) * | 2001-03-30 | 2002-10-09 | Sumitomo Chem Co Ltd | オレフィン重合用触媒、およびオレフィン重合体の製造方法 |
KR101113341B1 (ko) * | 2002-10-15 | 2012-09-27 | 엑손모빌 케미칼 패턴츠 인코포레이티드 | 올레핀 중합용 다중 촉매 시스템 및 이로부터 제조된중합체 |
US7541402B2 (en) * | 2002-10-15 | 2009-06-02 | Exxonmobil Chemical Patents Inc. | Blend functionalized polyolefin adhesive |
US7700707B2 (en) | 2002-10-15 | 2010-04-20 | Exxonmobil Chemical Patents Inc. | Polyolefin adhesive compositions and articles made therefrom |
CA2506144C (en) * | 2002-12-13 | 2011-09-20 | Dow Global Technologies Inc. | Olefin polymerization catalyst composition comprising group 13 amide derivatives |
EP1763542B1 (en) * | 2004-06-16 | 2011-04-06 | Dow Global Technologies Inc. | Technique for selecting polymerization modifiers |
KR101084677B1 (ko) * | 2008-05-14 | 2011-11-22 | 주식회사 엘지화학 | 올레핀 중합체의 제조방법 |
CN104677777B (zh) * | 2013-11-29 | 2017-10-27 | 中国石油化工股份有限公司 | 岩石残余含气量测试装置及其测试方法 |
EP3294692A1 (en) * | 2015-05-13 | 2018-03-21 | Sasol Performance Chemicals GmbH | Process for the oligomerisation of olefins by coordinative chain transfer polymerisation |
WO2023039514A1 (en) * | 2021-09-10 | 2023-03-16 | Dow Global Technologies Llc | Hydrocarbon soluble borate cocatalysts for olefin polymerization |
JP2024535749A (ja) * | 2021-09-10 | 2024-10-02 | ダウ グローバル テクノロジーズ エルエルシー | ポリオレフィン製造用ボレート共触媒 |
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US3311604A (en) * | 1961-02-04 | 1967-03-28 | Snam Spa | Process for polymerizing isoprene with a catalyst consisting of titanium tetrachloride and an aluminum hydride |
US3255169A (en) * | 1961-05-03 | 1966-06-07 | Exxon Research Engineering Co | Aluminum hydroaminate activators in olefin polymerization |
US3624118A (en) * | 1961-08-09 | 1971-11-30 | Olin Mathieson | Reaction products of alkali metal amides and trialkyl aluminum compounds |
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US3489736A (en) * | 1965-04-23 | 1970-01-13 | Showa Denko Kk | Polymerization of olefins |
US3723348A (en) * | 1967-03-20 | 1973-03-27 | Du Pont | Coordination catalyst |
BE759186A (fr) * | 1969-11-26 | 1971-05-21 | Inst Francais Du Petrole | Nouveaux catalyseurs de deshydrogenation des alcools secondaires |
DE2110195C3 (de) * | 1970-03-11 | 1975-07-31 | Snam Progetti S.P.A., Mailand (Italien) | Aluminiumverbindung, Verfahren zu ihrer Herstellung und ihre Verwendung bei der Polymerisation von Olefinen, konjugierten oder nicht-konjugierten Dienen oder Gemischen davon |
IT953411B (it) * | 1972-02-15 | 1973-08-10 | Snam Progetti | Produzione di lubrificanti sinteti ci da alfa olefine con un sistema catalitico ternario |
US4094818A (en) * | 1977-02-11 | 1978-06-13 | Exxon Research & Engineering Co. | Ziegler type catalyst system |
US4224182A (en) * | 1979-03-07 | 1980-09-23 | Exxon Research & Engineering Co. | Novel hindered alkyl aluminum amide cocatalysts |
US5055438A (en) * | 1989-09-13 | 1991-10-08 | Exxon Chemical Patents, Inc. | Olefin polymerization catalysts |
NZ235032A (en) * | 1989-08-31 | 1993-04-28 | Dow Chemical Co | Constrained geometry complexes of titanium, zirconium or hafnium comprising a substituted cyclopentadiene ligand; use as olefin polymerisation catalyst component |
US5057475A (en) * | 1989-09-13 | 1991-10-15 | Exxon Chemical Patents Inc. | Mono-Cp heteroatom containing group IVB transition metal complexes with MAO: supported catalyst for olefin polymerization |
US5064802A (en) * | 1989-09-14 | 1991-11-12 | The Dow Chemical Company | Metal complex compounds |
PL166690B1 (pl) * | 1990-06-04 | 1995-06-30 | Exxon Chemical Patents Inc | Sposób wytwarzania polimerów olefin PL |
BE1003968A3 (fr) * | 1990-11-08 | 1992-07-28 | Solvay | Solide catalytique utilisable pour la polymerisation stereospecifique des alpha-olefines, procede pour le preparer et procede pour polymeriser des alpha-olefines en sa presence |
JP3275211B2 (ja) * | 1991-05-20 | 2002-04-15 | ザ ダウ ケミカル カンパニー | 付加重合触媒の製造方法 |
US5721185A (en) * | 1991-06-24 | 1998-02-24 | The Dow Chemical Company | Homogeneous olefin polymerization catalyst by abstraction with lewis acids |
ES2111656T3 (es) * | 1992-01-06 | 1998-03-16 | Dow Chemical Co | Composicion de catalizador mejorada. |
US5374696A (en) * | 1992-03-26 | 1994-12-20 | The Dow Chemical Company | Addition polymerization process using stabilized reduced metal catalysts |
US5296433A (en) * | 1992-04-14 | 1994-03-22 | Minnesota Mining And Manufacturing Company | Tris(pentafluorophenyl)borane complexes and catalysts derived therefrom |
US6313240B1 (en) * | 1993-02-22 | 2001-11-06 | Tosoh Corporation | Process for producing ethylene/α-olefin copolymer |
US5470993A (en) * | 1993-06-24 | 1995-11-28 | The Dow Chemical Company | Titanium(II) or zirconium(II) complexes and addition polymerization catalysts therefrom |
CA2129794A1 (en) * | 1993-08-10 | 1995-02-11 | Toshiyuki Tsutsui | Olefin polymerization catalysts and methods of olefin polymerization |
US5486632A (en) * | 1994-06-28 | 1996-01-23 | The Dow Chemical Company | Group 4 metal diene complexes and addition polymerization catalysts therefrom |
-
1997
- 1997-07-18 WO PCT/US1997/012649 patent/WO1998003558A1/en active IP Right Grant
- 1997-07-18 EP EP97935016A patent/EP0914353B1/en not_active Expired - Lifetime
- 1997-07-18 PL PL97331324A patent/PL331324A1/xx unknown
- 1997-07-18 AU AU38051/97A patent/AU718544B2/en not_active Ceased
- 1997-07-18 HU HU9903962A patent/HU223376B1/hu not_active IP Right Cessation
- 1997-07-18 KR KR10-1999-7000417A patent/KR100466733B1/ko not_active IP Right Cessation
- 1997-07-18 US US08/896,897 patent/US6017842A/en not_active Expired - Lifetime
- 1997-07-18 JP JP10506330A patent/JP2000514858A/ja not_active Ceased
- 1997-07-18 CZ CZ1999239A patent/CZ293472B6/cs not_active IP Right Cessation
- 1997-07-18 TR TR1999/00080T patent/TR199900080T2/xx unknown
- 1997-07-18 CN CN97196607A patent/CN1092668C/zh not_active Expired - Fee Related
- 1997-07-18 BR BR9710511A patent/BR9710511A/pt not_active IP Right Cessation
- 1997-07-18 ES ES97935016T patent/ES2177995T3/es not_active Expired - Lifetime
- 1997-07-18 CA CA002261174A patent/CA2261174C/en not_active Expired - Fee Related
- 1997-07-18 DE DE69715213T patent/DE69715213T2/de not_active Expired - Lifetime
- 1997-09-27 TW TW086114148A patent/TW434271B/zh not_active IP Right Cessation
- 1997-10-08 AR ARP970104647A patent/AR010516A1/es unknown
Also Published As
Publication number | Publication date |
---|---|
HUP9903962A2 (hu) | 2000-03-28 |
AU3805197A (en) | 1998-02-10 |
US6017842A (en) | 2000-01-25 |
WO1998003558A1 (en) | 1998-01-29 |
BR9710511A (pt) | 1999-08-17 |
AR010516A1 (es) | 2000-06-28 |
DE69715213T2 (de) | 2003-04-30 |
AU718544B2 (en) | 2000-04-13 |
CZ293472B6 (cs) | 2004-05-12 |
HUP9903962A3 (en) | 2000-06-28 |
EP0914353B1 (en) | 2002-09-04 |
KR20000067938A (ko) | 2000-11-25 |
PL331324A1 (en) | 1999-07-05 |
EP0914353A1 (en) | 1999-05-12 |
ES2177995T3 (es) | 2002-12-16 |
CN1092668C (zh) | 2002-10-16 |
HU223376B1 (hu) | 2004-06-28 |
CZ23999A3 (cs) | 1999-04-14 |
JP2000514858A (ja) | 2000-11-07 |
DE69715213D1 (de) | 2002-10-10 |
CN1225644A (zh) | 1999-08-11 |
KR100466733B1 (ko) | 2005-01-24 |
CA2261174A1 (en) | 1998-01-29 |
TW434271B (en) | 2001-05-16 |
TR199900080T2 (xx) | 1999-04-21 |
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